Sensitization of photographic emulsions



Unit vS patemo SENSITIZATION or PHOTOGRAPI-IIC EMULSIONS Dorothy J. lieavera- Charles Wilson, and James L. Graham, Rochester, N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey a No Drawing. Filed Nov. 27,;19 s7, Ser. 699,198

' 17 Claims. (01:96-66) sentative quaternary salt sensitizing agent of that patent is the compound ethylene-biscxymethylpyridinitim; perchlorate. v

We have discovered certain compounds containing quaternary nitrogen. radicals which exhibit improved properties as sensitizing algents for silver halide emulsions. Emulsions containing the compounds of the ,invention are appreciably more stable than emulsions containing the mentionedquarternary compounds. Accordingly, upon the aging ofemulsions containing the new sensitizing agents, less fog is developed and the emulsion speed is maintained. Also, photographic emulsions containing the new quaternary nitrogen compounds maintain their speed over awiderrange of development conditions than do emulsions sensitized with previously .known alkylene-bis-pynidiniurnsalts such as decamethylene- LIO-b-is-pyridinium perchlorate Thus emulsions containing the'latter compound as a sensitizing agent can be expected to losean appreciable amount of speed'when developed with a developing solution of high sulfite consensitized with other quaternary salts such as that of the above Carroll invention.

It is interesting to note that Howe and Glassett British Patent 566,314 and Vanselow and James PSA Section B,

3640 (1953) have shown that certain quaternary nitrogen salts such as n-dodecylpyridinium bromide, n-dodecyltriethyl ammonium bromide, etc. are not efiective in increasing speed when development is carried out with a p-phenylenediamine as the developing agent such as used in color photography. In fact, it was shown by these workers that development with the p-phenylenediamine developing agent in the presence of the quaternary nitrogen salts retarded the development rate. The quaternary salts of the praent invention when employed in .the emulsions as sensitizing agents unexpectedly do not retard the development rate whendevelopment carried out with a pphenylenediamine.type developing'agent. T q t rn y a n i n ents, o t e i entin 2,944,898 Patented July 12, 1960 2. are bis-quaternary salts having Formulas A and B:

wherein n represents the integers 1 or 2, and therefore includes tetraand bis-urethanes of the general structures I and'II, respectively.

(I) QRNHCOOR'OCONHANHCOOROCONHRQ' (II) QROCONHANI-IQOORQ w p (B) QRNHCOOA(OCONHR' Q wherein n represents the integers 1 or- 2, andtherefore includes bisand mono-urethanes of the general structures 'III and IV, respectively.

(III) QRNHCOOAOCONHRQ' (IV) QRNHCOOAQ' f and ureas of the general structure VI.

(VI) R R2 R n the following two general In the above formulas Q and Q represent the smear different organic radicals containing quaternary nitrogen atoms such as trialkyl ammonium salt radicals, and eyelarnrn'onium. salt radicals e.-g. pyridinium salt radicals or quino-linium salt radicals. R and R represent the same or different, radicals, which may be alkylene, such as (CH and including a carbon chain separated by other atoms suchas O or S, e.g., --(CH ),,O(CH or (CH ),,S(CH n and n" being integers of from about -1' to 10. The total chain length of R and R' must be such that the number of atoms in the linear .chain joining-Q toQ' doesfinot exceed about 30. (The term atoms as used herein refers solely to the actual elements that compose the chain and not to any groups that these elements may carry. For example, -(CH is considered to be a 10-atom chain, the

hydrogen atoms being disregarded;

'( 2) s i z) 5- having less than about 14 atoms in the chain are not very useful sensitizing agents, the sensitizing activity of the compounds decreasing rapidly in compounds having less than about 14 or more than about 30 atoms in the'linear chain connecting Q and to Q. In a preferred embodiment of the invention, therefore, the compounds contain from about 14 to about 30 atoms in the chain.

In Formulas I and II above group A represents a linear chain of one or more atoms of carbon which may or may not contain sulfur, oxygen or nitrogen as an intermediate linkage.

In the above formulas the number of atoms comprising group A is limited by the number of atoms in R and R since as mentioned above the total number of atoms in the chain connecting Q to Q must not exceed about 30. Thus in Formula II, A may contain as many as 22 atoms in a linear chain when R and R are methylene groups. However, in such compounds where A represents an alkylene group, the linear chain of group A can contain only 2 to about 22 carbon atoms since it has not been possible to synthesize compounds in which A equals a CH group because the diisocyanate OCNCI-I --NCO required in the synthesis is not available.

v.Other chains of carbon, nitrogen, atoms represented by A are as follows:

V (cm) "1,l6 bis(pyridiniumperchlorate) -'(II)' 5,12-dia'za 3,14 dioxa 4,13 dioxohexadecane- 1 1 6-bi s (trimethylammonium-p-toluene sulfon ate) (III) 6,l3-diaza-4,15 dioxa 5,14 dioxo-octadecane- 1,18 bis(N-niethylpyridinium-p-toluene sulfonate) (IV) 8,15diaZa-6,17-dioxa-7,l6-dioxodooosane 1,22- bis (trimethylamrnoniurn-p-itoluene sulfonate) j "(V) 9,16 -diaza-7,18.- dioxa-8,17 dioxotetracosane- -1, 2 4-bis(pyridinium perchlorate) (VI) 13,20-diaza-11,22-dioxa 12,21 dioxodotriacon- 'tane-1,32-bis (pyridinium perchlorate) Y (VII) 3,10,17,24-*tetra2a-5,8,19,22-tet1'0xa 4,9,18,23- I tetrOXOheXacOsane LZG-biS (pyridinium perchlorate) f V INVERSE URETHANES' 1 .(VIII) 3,18-diaza 5,16 dioxa' 4,17 dioxoeic'osane- 1,20-bis(pyridinium perchlorate) (IX) 3-aza- 5-oxa-4 -Oxopentadecane 1,15 bis(pyridinium perchlorate) V p i UREAS AND N-SUBSTJTUTED UREAS XX 2,11-dioxo-1,3,10,12-tetrazadodecane-1,12 bis-I COMPOUND III COMPOUND IV nmi uonmoooNmcmn-izits 2 COMPOUND V oxygen or sulfur COMPOUND VII [osmi rwnumnooo oH.),o0cNH oH,)3-]2b1o,

. Z COMPOUND VIII I:otnu rwnamncOO OH,),]2b1o.

COMPOUND 1X 7 ctmiuommnooownowfiofimbio,

- COMPOUND X ONHCONHWHDP 25m The bis-quaternary lsalt" sensitizing agents described above may be prepared as illustrated below.

Ether 4 [(CH3)2N(CH2)5OOCNH(CH2)3]Z 'IOa solution of 5.2 g. (0.04 mole) of dimethylamino- -amyl alcohol in 100 m1. of'dry ether was added a solution of 3.4g. (0.02 mole) of.hexarnethylene diisocyanate; a exothermic reaction occurred. The mixture was refluxed for. three. hours and then pooled. A white solid (5.9" g., 69 percent); M.P. .84-8'5", precipitated from 'b1 i' n,-i ii J v r I analytical samplewajsobtainedupon recrystallizal-tion from ethanol-ether, M.P 84.084.5.

J [C SJ3 2)5O N 2)3]2 1 1 3 fIwenty-five'ml. of ethanol, 3.3 g. (0.008 mole) of 8,15 -d .iaga-j6,17 -dioxa 7,16 dioxodOcosane-l,22-bis(dimethylam'ine) (11498-20) and 3.2 g. (0.017 mole) of methylp-tqluenesulfonate, were heated at reflux for j-hp fihoursg Removal of the solvent, addition of ether, and vigorous scratching precipitated 6.1 g. (97 percent) of a white solid,- M.P. 2015420353.

analytical sample was obtained from ethanol-ether, 2030-2050".

5 .;Anal.Calc. fOI' C38H55N4O10S2: C, H, N, ,7.0;'S 8.0. -Found: C, 56.8; H, 8.4; N, 7.2; S, 7.9. The other symmetrical bis-urethanes having the general-Formula II above such as Compounds II and III to are prepared in a similar manner by use of the appropriate alcohol and diisocyanate'in the synthesis. In preparing the unsymmetrical bisurethanes the appropriate diisocyanate is reacted first with 1 mol of a dialkylamino- .alkyl alcohol followed by reaction with 1 mol of a different dialkylarninoalkyl alcohol, and the product subsequently quaterniz ed by treatment with, for example, methyl-p-toluene sulfonate.

V COMPOUND V 9,16#diaza-7,I8-dioxa-8,17-dioxotetracosane-1,24-dichloride 2c1 c,H, ,oH -OcN cH, ,NcO-

'- Cl CH2) GOOICNH (CH2) BNHCOO (CH2) 6C1 I Ten grams (0.06 mole) of hexamethylene diisocyanate and 16.2 g. (0.12 mole) of, hexamethylene chlorohydrin were mixedjtogetherand cautiously heated On' the steam 15 bath; when the'temperature reached 70, an exothermic The beautiful white crystals (22.3v g., 85 percent) melted at 85.0-86.5". In larger scale reactions, dry benzene may be used as the solvent for the isocyanate, and the chlonohydrin added slowly to this solution. Otherwise, the exothermic reaction cannot be controlled. The insoluble urethane was filtered from the benezene at the finish of the reaction x 5 An analytical sample was obtained frommethanol as a white crystalline solid of melting point 8687.5..'

Anal.-Calc. for C H N CI O C,54.5; H, 8.6; N, 6.4; Cl, 16.1. Found: C, 54.5; H, 8.7; N, 6.6; Cl, 15.9.

9,1 6-diaza-7,1 8-di0xa-8,1 7-dioxotetrocosarre 1,24-bis (pyridinium perchlorate) (1)2C5H5N 2 2Nao10. [CsH N (CH2)uOOCNH(CH2)3] (201-) 2C104- 1 A mixture of 50 ml. of dry pyridine and g. (0.023 mole) of 9,16-diaza 7,18 dioxa-8,17'-dioxotetracosane- 1,24-dichloride was refluxed for four hours. The excess pyridine was removed from the orange oil on the steam bath under vacuum. Ethanol was added and removed in the above manner to remove last traces of pyridine. The oily salt was redissolved in 25 ml. of ethanol and added to a solution of 6.3 g. (0.045 mole) of sodium perchlorate monohydrate in 25 ml. of acetone. The mixture was concentrated on the steam bath to about 30 ml., and the precipitated sodium chloride filtered off.

The solution was slowly saturated with ether while cooling in a Dry Ice-acetone bath. The precipitated white granular solid was dissolved in a minimum of methanol, and acetone slowly added while chilling in a Dry Iceacetone bath. The product was obtained as a crystalline white solid weighing 12.0 g. (73 percent) and melting at 63-65 The analytical sample was obtained from a methanolacetone mixture and melted at 63-65". AWL-C316. f0]: C oH4 N4C12012; C, H, 6.6; N,

7.7; Cl, 9.8. Found: C, 49.6; H, 6.8; N, 7.8; Cl. 10.7.

. V COMPOUND 3,18 diaza-5,16-dioxd-'4,1 7-dioxoeic0sane-1 ,ZO-dichloride A mixture of 10 g. (0.057 mole) of 1,10-decamethylenediol and 12.2 g. (0.116-mole)of fi-chloroethyl isocyanate was cautiously heatedon the steam bath. At 70 ,an exothermic reaction took place which was controlled by cooling with ice water. After the exotherm had subsided, the solid was heated at 130 for three hours to insure complete reaction. The solid was recrystallized from 200 ml. of methanol; 19.6 g. (89.5 percent), melting point l07.5-l09.5.

If this reaction is run on larger scale, an inert solvent such as benzene or toluene should be used as the violently exothermic react-ion cannot be controlled without solvent. The desired product can then be filtered from the resulting slurry in pure form.

-An analytical sample was obtained by recrystallization from methanol, melting point 106.5-.108.5.

Five grams (0.013 mole) of 3,18-diaza-5,16-dioxa-4,17- dioxoeicosane-1,20-dichloride and 50 ml. of pyridine were vigorously refluxed for three hours. The excess pyridine was removed from the oil under vacuum on the steam bath, until no odor of pyridine remained. The oil was dissolved in 25 ml. of methanol and added to a solution of 4.0 g. (0.0286 mole) of sodium perchlorate in 50 ml. of acetone. The slurry was heated on the steam bath for 30 minutes, and the sodium chloride removed by filtration. The filtrate on chilling gave seven grams of a white solid, melting point 8090. The crude solid was recrystallized twice from alcohol-acetone, 5.3 g.(61 percent). It melted at l20-.122.5 when placed on the hot stage at Anal.Calc. for C26H40N4O12C12: C, H, N, 8.3; Cl, 10.6. Found: C, 46.1; H, 6.0; N, 8.3; Cl, 10.9.

A mixture of 12 g. of 5,12-diaza-3,14-dioxa-4,13-dioxohexadecane -1,16-diol [prepared as described by Petersen, Ann., 562, 220 (1948)] and 9 g. of B-chloroethyl isocyanate was heated on the steam bath until a clear melt was obtained. The mixture was allowed to stand at 70 for 15 hours, though it had set to a solid in about onehalf hour. The crude product was recrystallized from a large volume of methanolIto yield 15 g. of 1,26-dichloro- 3,10,17,24 tetraza-5,8,19,22-tetroxa 4,9,18,23 tetroxohexacosane of M.P. 159-461".

Anal.Calc. for C H O N 'Cl C, 42.9; H, 6.4; N, 11.1; C1, 14.1. Found: C, 43.5; H, 6.4; N, 10.7; Cl, 14.0.

A solution of 8.6 g. of the dichloro compound obtained in 30 ml. of pyridine was refluxed for 2 hours. An oil separated from the solution during the heating. The excess pyridine was removed under reduced pressure and the residue dissolved in methanol. tion was treated with a solution of 6 g. of sodium perchlorate in methanol. After warming'for 15 minutes, the sodium chloride that separated was removed by filtration. 'Ihe filtrate was concentrated to a small volumeand the quaternary salt precipitated as a gum by the addition of ether. The liquid was decanted from the gum and the "latter was triturated with ether. The ether was decanted total solid (7.5 g.) was recrystallized first from acetone and then from methanol-ether. In all cases of recrystallization the product first separated as a guru which set to a solid on chilling. Final yield, 5 g.

AnaL-Calc. for C H O N Cl C, 42.8; H, 5.4; N, 10.7; C1, 9.0. Found: C, 42.0; H, 5.2; N, 10.1; C1, 10.5.

In a similar manner other symmetrical tetra-urethanes having the general Formula I above may be prepared using the appropriate alcohols and isocyanates. In preparing the unsymmetrical tetra-urethanes where R and R are different the diol compound is first reacted with 1 mol of the appropriate haloalkyl isocyanate followed by reaction with 1 mol of a different haloalkyl isocyanate.

COMPOUND IX 3-aza-5-0xa-4-0x0pentadecane-I,15-dichl0ride Cl(CH NCO-[-HO(CH Cl- Cl(CH NHCOO(CH Cl Decamethylene chlorohydrin (19.3 g, 0.10 mole) and 10.5 g. (0.10 mole) of 2-chloroethyl isocyanate were added together giving a mildly exothermic reaction. After the exotherm had subsided, the oil was heated on the steam bath for five hours. Upon cooling, 2. white crys- This solutraces of inorganic salt removed by filtration.

. 7 talline' mass weighing 29.5 g. (99 percent yield) and melting'at 32-35; 'was obtained. Y 1

The analytical sample (M.P. 40.5-43.0?) was obtained from ether upon chilling in a Dry-Ice-acetohe bath. f AndL- Calcifor C H Cl NO C; 52.3; H 8.4; N, 4.7; Cl, 23:8. Found: C; 52.9; H, 8.5; N, 4.9; Cl; 24.0.

' peltchldrdte) Twenty-five ml. of dry pyridine and 5 .0 g. (0.017 mole) of 3-aza-5-oxo-oxapentadecane-1,15-dichloride were refiuxed for three hours. Excess pyridine was, removed on the steam bath under vacuum. The oil'was then dissolved in methanol and this solventremoved under vacuum.

The resultant yellow oil was dissolved in 25 ml. of

methanol and added to a solution of 5.5 g. of sodium perchlorate' monohydrate in 25 ml. of acetone. The

'slurry was concentrated to one-half of the original volume and the inorganic salt filtered off. The solvent was removed from the oil, the oil dissolved in acetone; and the All attempts to obtain a crystallineproduct were unsuc'cessful. The 'product was isolated as a water-solubleyellow oil weighing 6.5 g. (76.5 percent yield). 7

COMPOUND XI 4,17 di0x0-3,5,16,18-tetrazaeic0sane-1,ZO-dichlofide 8-Cbloroethyl isocyanate (10.6 g., 0.10 mole) was dis.-

solved in 400 ml. of dry ether in a one-liter flask equipped with stirrer and condenser. With 'efiicient stirring a solution of 8.6 g. (0.05 mole) decamethylenediamine in 200 ml. of dry benzene was slowly added. A dense white solid began precipitating immediately. After the complete addition of the diamine solution, the slurry was refluxed for twojhours, then cooledand filtered. ,"Th'e whitesolid was 'washedwith ether and air dried; yield,

11.9 g. .(62 percent),mlting pointl58j-l62. An analytical sample of the urea was obtained from'a large volume of methanol, melti'ng point 1625-165 .5

Anal.Calc. for C H N O Cl 'C, 50.1; H, 8.4; N,

14.6; C], 18.5. Found: C, 50.6; H, 8.4;,N, 14.6; CI, 17.8.

A mixture of 50 ml. of dry pyridine, 20 ml. of absolute ethanol, and 5.7 g. (0.015 mole) of 4,17-dioxo-3,5,16,18-

tetrazaeic'osane-l,20-dichloride was heated to reflux for two hours. The solvents were removed on the steam bath under vacuum. The .oil was slurried several times with ether and the ether decanted in order to remove traces of pyridine.

The pyridinium chloride was dissolved in ml. of., 'methanol, and a solution of 5.0 g. (0.036 mole) of sodium perchlorate monohydrate in 25 ml. of acetone added. The mixture was heated on the steam bath; immediately a dense solid consisting of bis-pyridinium perchlorate and .s odium chloride separated. Alarge volume of ether-was 8 added to the chilled'slurry andthe solid filtered 01f. The solid-was 'dissolvedin 225 'ml. of hot aqueous methanol (1:2). Upon chilling, 5.8 g."-of a'cream-colored solid precipitated; melting point 182.5-186.0. Concentration ofthe filtrate gave an additional 2.2 glof product, melting point 180-185". Total yield, 80 percent. P in-analytical sample was preparedby recrystallization from. a 'metha nol wat'er so1ution,'melti'ng point 182-185.". Analysis. Calc. for'CigHr N O Cl z C, 46. 6; H,.6.3; N, "1'2.'5 Cl; Found: C, 46.6; H, 6.5; N, 12.8; C1,

The following .examples illustrate the use of the bis;- quaternary salts of the invention: in photographic emul- A, high-speed bromoiodide emulsion was prepared chemically sensitized 'withl'sulfur and gold compounds and optically sensitized with a cyanine dye. of the bis-quaternary nitrogen compound shown in Table I below were added to samples of the emulsion alone and together with .an -azaindene stabilizing agent. The emulsion samples were then coated, exposed on a sensitometer and developed for 5 minutes at 68 F. in the developergiven. below. The. speed, gamma and fog values obtained; by'sensitornetric evaluation of the developed samplesare'al soshownin the table. The speed values shown are lexpress ed as" 100 (l-log ,E) where E is .the exposure in" metercandlefsieconds required to producein the emulsion'a density. 0.3 above fog.

Water, cc 500 Elon V rams" 2.5 .Sodium ;sulfite anhydrous do 30.0 Hydroquin'one, '..e do 2.5 Sodium' metaperb'orate-.. do 100 Potassium, bromide do 0.5

F 1. ITABLEI Number I Feature 7 Speed v Fog 131353..-- Control are 1.23 0.15 137356 5, 12-Dlaza-3, 14=d1oxa-4,131diox0hexa- 321 1.24 .18 H deeane-lg 'l6-bis(trimethylammoniFm-lp-toluenesulfonate) (II) 0.75' f gmo. i 1373614.. 4-Hydro'xy-6-methyl-1, 3;3a, 7-tetra-'- 1 325' 1.13 -.15

zaiudene (XXX). 3.0 g./1nol. 137366.-.. (XXX) 3.0 g./m0l+(II)0.-75g./m0l 328 1.24 .15 137357. txx x 3.0 g./1nol l-(I I) 2.2 5 g./l nol Emi I An emulsion was-provided as in Example 1 and the additions shown in Table; 2 were made to samples of the emulsion. Sensitometn'c evaluation made as describedinExample 1 gave the results shown in the table.

TABLE 2f.

Number. Feature Speed 1 Fog 140911--" Control 318 l. 29 0. 20 140915---- 9, 16-Dlaza-7, 18-d1oxa-8, 17-d10X0- 340 1. 27 26 tetracosane-l, 24-bis(pyrid iniun1 i Perchlorate) (V) 0.75 gJmol. 140921.--. 4-Hydroxy-6-methyl-l, 3, 3a, 7-tetra- 325 1. 31 .19

zalndene (XXX) 3.0 g./mol. 1409294 (XXX) 3.0' g./I nol+ (V) 0.75 g./m0l 344 1. 22 24 140930--.- (XXX) 3.0 gJmol-l- (V) 2.25 g./mo1. 353 1. 35 24 Example 3 An emulsion was provided as in Example 1 but with the addition to samples of the emulsion of the compounds shown in Table, 3. Processing was carried out as in Example 1 for evaluating the emulsion sensitivity and other characteristics of the emulsion.

The amounts BI Number Feature Speed 7 7 Fog i 1; 308 1.30 ,0.17 3, 10,17, 24-Tetraza-5, 8, 19, 22 -tetra-. 322 1.38 .16 axe-4, 9,18,23-tetroxo-1,26-bis(pyridinlium perchlorate) (VII) 0.75 g./ V v mo '4-Hyd roxy-6-methyl-1, 3, 3a, 7-tetr'a- 317 1.35 -14 zaindene(XXX) 3.0 g./mol'. 1 i 152000- (XXX) 3.0 g Jmol-l-(VII) 0.75 g./rno1.; 322 1. 38 16 1520011 (XXX) 3.0 g./mol-l-(VII) 2.25 g./n1ol.. 1 328 1.32 .15

. 7 Example 4 An 'ernulsion was prepared and tested as" shown in Example r nsing" the bis-quaternary compound shown in Table 4. The dataof this example shows that additional speed increase'can beetfected by using a combination of a bis-quaternary compound of the invention such as 'lllaan'd' a polyethylene glycol XXXI, i.e., a polyethylene oxide or average molecular weight of 1500 (PEG 1500).

TABLE 4.

-Number .Feature Speed 7 Fog 146237.; Control 317 l. 30 0. 17 146242.-.. 6, 13-Diaza-4, 15-tlioxa-5, l4- dioxo- 331 1.32 .20

octadecane-l, 18-bis(' -pyridinium J1; m/ethti-p-toluenesulfonate) (III) 0.3 1 r, g. 1110 146245.... 4-Hydroxy-6-methyl-1, 3, 3a, 7-tetra- 328 1.35 .16

zaindene (XXX) 3.0 g./mol. 146258..-- (XXX) 3.0 g./ml+(III) 0.3 g./mol-- 335 1.31 .20 146259..-. (XXX) 3.0 gJmol-l- (III) 0.75 g./rn0l.-. 337 1. 13 19 446263.... (XXX) ?.0g1./mol+PEG 1500 (XXXI) 346 1.06 .18

0.75g.mo. 146269..-. (XXX) 3.0 g./mol-l-(XXXI) 0.75 g./ 351 1.01 .20

- I moH- (III) 0.3 gJmol.

. -Exttmp le An emulsion "was prepared and tested as in Example An emulsio'n was prepared andtested as in Example l.using.the' bis-quat ernary urea compound X.

TXBLE G lvuinber Feature Speed 7 Fog 147490---. oontroL-.. 315 in 0111 147481--.. .Hexamethylenebi [3-(2-ureidopyri- 315 1.15. .15 dinium metho-p-toluenesulfonate)]' (X) 0.75 g./m0l. 1 147491.... 4-Hydroxy;6-methyl-1, 3, 3a, 7- tetra- 321 1. 25. .17

zaindene (XXX) 3.0 gJmol. (XXX) 3.0 g./n101+(X) 0.3 g./mol..--. 322. 1.09 .17 (XXX) 3.0 g./mol-l-(X) 0.75 g./mol...- 325 1.06 15 147505.... (I???) /3.0 g1./mol+PEG 1500 (XXXI) 343 1.05 .17

g.mo." 147508-.-- (XXX) 3.0 g./mo1+ (XXXI) 0.75 g. 343 1.01 .17

i h molj- 0.75 gJmol.

A fast bromoiodide emulsion was chemically sensitized with sulfur andgoldcompounds and optically sensitized with-a combination of cyanine dyes. In addition, 3.0 gramsp'ermole of silver halideof 4-hydroxy-6-methyl- 1,3,3a,-7-'tetrazaindene and 0.75 gram per mole of silver halide of a polyethylene oxide of average molecular weight 1500 were added. The amounts of the compounds shown in Table 7 were then added and the .ernulsions coated. Testing was carried out as in Example .ljupon'the' freshlycoated emulsion samples and other v samples of each'emulsion werejincubated for 1 Week at f. 120 and percent relative humidity. Still other samples 'of each emulsion WBI'C'SIOI'Ed under room conditions f7 8 F: Keeping and developed with the same developing'solution given in Example 1 with the result shown "in Table 7. Consideration of the fog data in the table shows that the emulsions containing the compoundV of the invention were more stable than the emulsions containing the alkylene bis-pyridinium compound of the prior art;

following table.

TABLE 5 Number Feature Speed 1 Fog 149878.--. Control 305 1.22 0.10

149885.... 3,18-Diaza-5,1'6-dioxa-4,17- 327 1.26 .12

. dioxoeioosane-l, 20-bis(pyridinium perchlorate) (VIII) 0.75 g./rn0l.

149888.... 4-Hydroxy-6-methyld, 3, 3o, 7- tetra- 313 1.10 V .10

V e zaindene (XXX) 3.0 gJmel.

149907..-. (XXX) 3.0 g./mol+ (VIII) 0.75 g./1'110l 324 1. 03 11 149908."... (XXX) 3.0 g./mol+ (VIII) 2.25 g./m0l..' 325 1. 05 12 149911.... (XXX) 3.0 g./mol+PEG 1500 (XXXI) 333 1.02 .12

'--' 0.75 g.mol. I

149912...- (XXX). 3.0 g./n1o1+(XXXI) 0.75 g./ 337 1.17 .14 v mol-l-(VIII) 0.75 g./mo1. I

.. TABLE 7 Fresh Tests Incubation 1 3 Months 78 wk. F. Keeping Number Feature CR Fog CR 7 Fog OR 7 Fog :S p. Sp. Sp. 1

147810..-- Control 342 1.12 0.15 343 1.01 0.16 337 1.05 0.16 147820..-- Hexadecamethylene-1,16-bis(pyridin- 1356 1.10 .24 359 1.10 .22 353 1.20 .20

ium perchlorate) 0. g/mol AgX. 147821..-. Hexadecamethylene-1,16- bis(pyridin; "356 1.24 .30 350 1.02 .34 359 1.23 .26

ium perchlorate) 0.3 g/mol AgX. 147822.-.- Hexadeca-methylene-1,16 bls(pyridin 355 1.17" .29- 345 .90 .48 356 1.23 I .31

. ium perchlorate) 0.6 g/mol AgX 147848..-- 9,16-Dina-7,18-dlOXa-8,17-dlox0tetra- 351 1. 10 .19 356 1.17 .17 350 1.32 .17

cosane 1,24 his(pyridinlum perchlorate) (V) 0.45 g./mol AgX. 147849..-. 9,16-Diaza-7,18-dioxa-8,17-dioxotetra- 354 1.18 .18 359 1.10 .18 334 1.30 .20

cosaue 1,24 his(pyridinium perchlorate) (V) 0.75 g./mol AgX. 147850..-- 9,16-Diaza-7,18-di0xa-8,17-dioxotetra- 355 1.29 .19 361, 1.28 .19 339 1.42 .17

, cosane 1,24 bis(pyridinium perchlorate) (V) 1.2 g./rn0l AgX.

'1 using the inverse urethane VIII as shown in the Example 8 The use of the bis-quaternary salts of the invention in color photography is illustrated in this example.

A sulfur and gold sensitized gelatino silver bromoiodide emulsion was ripened to maximum sensitivity. To this emulsion was added an optical sensitizing dye that extended the light sensitivity to 6000-7000 A. and a hydrophobic cyan 'color former suitably dispersed in a high boiling organic solvent.- Aportion of this liquid emulsion received no further treatment; to another portion'was added one of thecompounds described below. Both portions were coated on film support, and the dry films were -'exposed--to red light in an intensity scale sensitometer. I The exposed films were processed inthe reversal Color Process land the-5248 negative Color ProcessZ' with the assess 11 results shown in the follq jng table. The Color Process 2 was carried out as described 'by Hanson and Kisner JSMPTE 61 667-701 (1953) forthe Color Negative Film, Type 5248-,invol-ving the steps of color 'developmenflfixation, silver bleaching and final fixation. Color Process 1 was carried out at 75 F.-as follows:

(1) Negative development 10 '(2) Reversal flash exposure (3) Color development l (4) Silver bleaching 8 (5) Fixing Y 3 The negative developer had the following composition: Water, 90 F. (32 CL) 'liter 1.0 Sodium hexametaphosphate "grams" 2.0 N-methyl p-aminophenol sulfate do 6.0 Sodium sulfite, desiccated d0; 50.0 Hydroquinone ...d0 6.0 Sodium carbonate,monohydrated do 35.0 Potassium bromide d0 2.0 Sodium thiocyanate do 1.5 0.5% solution (6-nitrobenzimidazole nitrate) cc 12.0 0.1% solution of potassium iodide ..cc 10.0

I he color developing solution above-had the following composition:

As indicated in the above examples, it may be to incorporate a stabilizing agent into the emulsion sensi- 12 Process 2 of Example 8 and a multilayer color film having couplers in the emulsion layers was developed therein,

speed increase was obtained panticularly for the red and green sensitive emulsion layers.

desirable tized with the bis-quaternary salts of the invention to reduce fog to normal levels. Azaindenes particularly suitable for this purpose arethose described in the Carroll et a1. U.S. patent application Serial Nos. 627,135 and 627,136, filed December 10, 1956, for example, thefollowing: 5 carboxy-4-hydroxy-l,3,3 a,7-tetraza.indene, 1,2.-

methyl-l,3a,7-triazaindene, 4-hydroxy-2y-hydroxypropyl- 6-methyl-l,3,3a,7-tetnazaindene and 4-hydroxy-.2( *PYIi' dyl -6-methyl-1,3 ,3 a,7-tetrazaindene.

The preparation of silverhalide emulsions involves three separate operations: (1) the emnlsification and digestion or ripening of the silver halide, (2) the freeing of the emulsion from aqueous soluble salts usually by washing, (3) the second digestion or after ripening to obtain increased sensitivity (Mees, The Theory of the Photographic Process, 1942, page 3). The sensitizing agents may be added at any stage, preferably after the final digestion.

j The photographic emulsions which we use are of the developing-out type and best results have been obtained with gelatino-silver .brornoiodide emulsions. However, emulsions of varying silver halide content may be used.

The emulsions are chemically sensitized by any of the accepted procedures in addition to sensitizing with the bis-quaternary salts of the invention. The emulsions may be digested with naturally active vgelatimor sulfur. compounds may be added such as those described in Sheppard U.S. Patents 1,574,944 and 1,623,499, and Sheppard and Brigham U.S. Patent 2,410,689.

The emulsions may also be treated with salts of the noble metals such as .ruthenium, rhodium, palladium,

, weight greater than 100. Representative compounds are ammonium chloropalladate, potassium chloroplatinate and sodium chloropalladite, which are used for sensitizing in amounts below that which produces any substantial fog inhibition, as described in Smith and Trivelli U.S. Patent 2,448,060, and as anti-foggants in higher amounts, as

:Water, 70 man F. 21 to 27 0. .na 1.0 Benzyl alcohol 0P 6.0 Sodium hexarnetaphosphate grams 2.0 Sodium sulfite, desiccated "do"..- 5.0 Tr-isodium phosphate do 40.0 Potassium bromide gran1.., 0.25 0.1% solution of potassium iodide ..ec 10.0 Sodium hydroxide "grams-.. 6.5 (4 amino N ethyl-N-B-methane' sulfonamido- -ethyl)m -toluidine .sesquisulfate monohydrate v grams-.. 11.33 Ethylenediamine sulfate "do-.." 7.8 Citrazinic acid (2,6-dihydroxyisonicotinic acid) grams-.. 1.5

' :The silver'bleaching solutionabove had'th'e following composition: I Water 90 F. (32 C.) liter 1.0 Potassium dichronrate grams 5.0 Potassium ferricyanide ..;...do 70.0 Potassium bromide i do.... 20.0 The fixing baths above had the following composition Water, 80 F. (27 C.) liter.. 1.0 Sodium thiosulfate grarns 150.0 Sodium bisulfite V g I do 20.0

TABLE 8 Color Process 1 Color Process 2 Number Feature (Reversal) (5248 Negative) Speed Increase Speed Increase (A Log E) 1 (A Log E) 19360 Control. 19365"... Ctznpiund I, 2.0 g./mole I. +0.16 +0.15 195400." Con troll I 19549.-- cinggtund YI, 2.0 g./mole +0. 18 +0. 18

l Determined by measuring the shift of the reversal dye curve on the Log E axis'at a given density below maximum density.

1 Determined by measuring the shift of the negative dye curve on the Log E axis at a given density above minimum density.

The bis-quaternary salts described above can be used in emulsions in the manner of the above examples in concentrations of the order of about0.02 to 4 grams per mol of 1silver halide. l i"? *1 Y a; he emulsions may also be developed inthe presence of '.the bis-quaternary salts by; incorporating the salts into .a 'edeveloper-a solutionz; For example, when; compound VI described in Trivelli and Smith U.S. Patents 2,566,245 and 2,566,263.

The emulsions may also be chemically sensitized with gold salts as described in Waller and Dodd U.S. Patent 2,399,083 or stabilized with gold salts as described in Damschroder U.S. Patent 2,597,856 and Yutzy and Leermakers U.S. Patent 2,597,915. Suitable compounds are potassium chloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride andZ-aurosulfobenzo-thiazole methochloride.

The emulsions may also be chemically sensitized with reducing agents such, as stannous salts (Carroll U.S. Patent 2,487,850), polyamines such as diethylene triamine Lowe and Jones U.S. Patent 2,518,698), polyamines such as spermine (Lowe and Allen U.S. Patent 2,521,925), or bis-(Beaminoethyl) sulfide and its water-soluble salts (Lowe and Jones U.S. Patent 2,521,926).

The emulsions may also contain polyalkylene oxides and derivatives thereof such as the polyethylene glycols, in addition to the bis-quaternary compounds of the invention. Suitable polyalkylene oxides and polyalkylene oxide derivatives are described in Blake U.S. Patent 2,441,389,,Mayl1, 1948, Blake et a1. U.S. Pa'tentsZfQO;

13 532, May 21, 1946, 2,423,549, July 8, 1947 and Jennings et al. U.S. Patent 2,577,127, December 4, 1951.

Other compounds useful for suppressing the fog level of the emulsion sensitized with the bis-quaternary compounds of the invention include the mercury compounds of Allen et al. U.S. Patent 2,728,663, Carroll and Murray Patent 2,728,664 and Leubner and Murray U.S. Patent 2,728,665, granted December 27, 1955, and the organic salts of U.S. patent application Serial No. 493,- 2,784,090, granted March 5, 1957. 1

Other stabilizing agents may be added to the emulsions containing the bis-quaternary salts such as the metalinorganic salts of U.S. Patent application Serial No. 493,-

047,.filed March 8, 1955 by J. E. Jones.

"The chemicalsensitizing agents and other addenda which we have describedmay be used in various kinds of photographic emulsions, e.g., various silver salts may be used as the sensitive salt such as silver bromide, silver iodide, silver chloride or mixed silver halides such as silver chlorobromide or silver bromoiodide. V

The dispersing agent for the silver halide may be gelatin or other hydrophilic material such as collodion, albumin, cellulose derivatives or synthetic resins.

Since the coupler-containing emulsions sensitized as described with the bis-quaternary salts are adapted particularly for use in color photography, they will ordinarily comprise the emulsion layers of multilayer color films which emulsion layers are customarily differentially sensitized to the primary regions of the visible spectrum and contain coupler compounds producing dye images of colors complementary to the sensitivity of the emulsion layers. In a representative color film, one or more of the differentially sensitized emulsion layers may be sensitized with the bis-guaternary salts, and in a typical example emuls'ionssensitizedto the red, green and blue regions of the spectrum are super-imposed on the support in that order and contain cyan, magenta and yellow colorforming coupler compounds respectively. p A yellow filter layer such as yellow colloidal silver is advantageously interposed between the blue and green-sensitive emulsion layers. I

Since the'the emulsion layers sensitizedwith the bisquatcrnary salts of the invention may contain coupler com ounds they can be readily processed by well known methods to yield color negatives directly or positive images bymeans of well known reversal processes. That is, after initial exposure of the emulsion to a subject a developer of the p-phenylenediamine type Will produce a .colored image negative in respect to the subject. Like- }wise,'if development of theemulsion layer is first carried --out with a non-color-forming developer followed by reversal exposure'of the residual silver halide and then color development, a colored positive is obtained as described in the examples above.

The coupler compounds used in the emulsion layers sensitized with the ionic polyalkylene oxide derivatives, are any of the well known compounds which combine with the oxidation product of primary aromatic amino (p-phenylenediamines) silver halide color developing agents to form dyes, for example, the phenolic couplers of U.S. Patents 2,266,452, 2,362,598, 2,589,004, 2,474,- 293, 2,521,908, 2,423,730 and Fierke U.S. patent application 476,561; the pyrazolone couplers of U.S. Patents 1,969,479, 2,369,489, 2,600,788, 2,618,641, 2,511,231 and the open chain reactive methylene couplers of U.S. Patents 2,298,443, 2,652,329, 2,407,210, 2,271,238 and McCrossen et a1. U.S. patent application Serial No. 575,099, filed March 30, 1956. Likewise, the emulsions may contain colored color-forming couplers as described in U.S. Patents 2,521,908, 2,706,684, 2,455,169, 2,694,703, 2,455,- 170 and 2,453,661.

The couplers may be dispersed in the emulsion layers by means of an oily coupler solvent according to the methods of U.S. Patents 2,304,940 and 2,322,027. However, if as may be the case, the couplers contain solubilizsoluble in alkaline solution, the oily coupler solvent may be dispensed with and the couplers can be added to the emulsion from aqueous solutions as their alkali metal salts.

What we claim and desired to secure by Letters Patent of the United States is: i

l. A photographic silver halide emulsion containinga quaternary ammonium salt having a general formula of the class consisting of wherein R R and R represent lower alkyl groups,-Z

represents the atoms necessary to complete a heterocyclic nucleus ot the class consisting of pyridinium and quinoliniurn', R and R each represent alkylene groups linked to the quaternary nitrogen atoms of said radicals, R .represents a member of the class consisting of a hydrogen atom and an alkyl group of from 1 to 4 carbon atoms, n represents a positive integer of from 1 to 2, .A represents'a member of the class consisting of and wherein n and n" represent positive integers of.from

about 1. to 10, there being from about 14 to about 30 ato'm's'present in the shortest linear chain of atoms linking saidquaternary nitrogen atoms.

2. A photographic silver, halide emulsion containing a quaternary ammonium salt having the general formula QRNHCOOROOCNHANHCOOR'OCONHRQ' wherein Q and Q represent radicals of the, class consistwherein and Q represent radicals of the class consist,-

R represent lower alkyl groups, Z

wherein R R and represents the atoms necessary to complete a heterocyclic t-nucleus' of the class consisting of pyridinium and quinoli- I QRNHCOOAQf I wherein Q and Q each representpradicals of the class conwherein R R and R represent lower alkyl groups, Z

.T'represents the atoms necessary to complete a heterocyclic .nucleus of the class consisting of pyridinium and quinolinium, R and A each'represent alkylene groups, there being. from about 14' to about 30 atoms present in the shortest linear chain of atoms linking the quaternary lnitrogen atoms of said radicals.

wherein n and n' represent positivejintegers of from jabout'l to -10,' therebeing from aboutli14 to"about 3 0 atoms presentin the shortest linear chain of atoms linking said'qua'ternary nitrogen atoms. p I a i 6.-A photographic silver halide emulsion containing the compound 5,l2-diazag3 ,14diorra 4;13-dioxo-hexadecane-l,16-bis(trimethylammonium p-toluene sulfonate). Z 7'. A photographic silver halide femulsioncontaining the. compound 6',l3-diaza-4,lS-dioxoS,l4rdioxo-octadeclane- 1,l8:bis(N-methylpyridinium p-toluenesulfonate). 7

5. A method of increasing the speed of a silver halide emulsion layer which comprises developing said emulsion in the presence of a quaternary ammonium salt having a formula of the class consisting of wherein R R and R represent llower allryl groups, Z represents the atoms necessary to complete a heterocyclic nucleus of the class consisting of pyridinium and quinoto the quaternary nitrogen atoms of said radicals, R represents a member of the class consistingpf a hydrogen atom and an alkyl group of from 1 to 4 carbon atoms,

. n represents a positive integer of from 1 to 2, A represents a member of the class consisting of .linium, R and R each represent alkylene groups linked 8. A photographic silver halide emulsion containing the c'omp'oun'd'9,16ediaza-7,18;dioxa 8, 17 dioXotetracosane- "1,24-bis(pyridinium perchlorate). a 9. A photographie silver halide-emulsion containing thevcompround 3,10,17,24-tetrazai-5,8,l9,22atetroxa-4,9,l8, 23-tet'roxohexacosane-1,26-bis(pyridinium perchlorate) 10. A photographic silverlhalide emulsion containing the compound 3,1 8-diaza 5,16-dioiia 4,17-dioiroeicosane- 1,20 -bis(pyridinium perchlorate). 1

,ll.':The emulsion of claini'2 further containing a cou- ,pler compound reactive with theoxidation products of a .phenylenediamine silver halide developing agent to form a' dye. 7

12. The emulsion of claini 3 further containing a con- ,pler compound reactive with the oxidation products of a phenylenediamin silver halide developing agent to forin 13. The emulsion ofclairn-4 further-containing a coutpler compound reactive with the oxidation products of a -,phenylenediamine silver halidedeveloping agent to form .radye. ::14 The emulsion of claim Z azaindene stabilizing agent; q V

15. 'Ihefemulsionofj claimv 3; further-containing an azaindene stabilizing agent. A H

?16." The emulsionof claim A further containing an containing an Carroll et'a1.; ;f' June 30, 1942 2,419,975 Trivelli et al. May 5, 1941 2,784,090 Carroll Mar. 5, 195 7 JFOREIGN: PATENTS 115,971

UNITED STATES PATENT OFFICE CE TIFICATE OF CORRECTION Patent Noa 2,944 898 July 12 1960 Dorothy J, Beavers et alo It is hereby certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 13, line 9 strike out "salts of U030 patent. application Serial No, 493 and insert instead mercury compounds of Carroll et al U,Sa patent Signed and sealed this 4th day of April 1961..

(SEAL) A ERNEST W. SWIDER ARTHUR W. CROCKER Attesting Oflicer A ting Commissioner of Patents 

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A QUATERNARY AMMONIUM SALT HAVING A GENERAL FORMULA OF THE CLASS CONSISTING OF 